JP2021507056A - Dithiocarbonate-containing polyol as a polymer polyol stabilizer - Google Patents

Abstract

The present invention relates to novel macromers containing dithiocarbonate (or xanthate) groups, novel preformed stabilizers containing macromers, and novel polymer polyols containing novel macromers and / or newly preformed stabilizers. The present invention also relates to a method for preparing these materials. Other aspects of the invention include a foam containing a novel polymer polyol and a method of preparing a foam containing a novel polymer polyol.

Description

The present invention relates to novel macromers, novel preformed stabilizers containing novel macromers, novel polymer polyols containing novel macromers or novel preformed stabilizers, and methods of preparing these materials. The present invention also relates to foams prepared from these novel polymeric polyols and methods of preparing these foams.

Polymer polyols, also known as filled polyols, are viscous fluids containing fine particles dispersed in the polyols. Examples of solids used include styrene-acrylonitrile copolymers and polyureas. The solid is typically prepared by in situ polymerization of the ethylenically unsaturated monomer in the base polyol. Polymer polyols are commonly used in the production of polyurethane foams, especially flexible polyurethane foams.

Macromers have been known to stabilize polymer polyols by copolymerizing with one or more ethylenically unsaturated monomers (eg, styrene and acrylonitrile) and have been used therefor. Due to their similar chemical composition, the tails of one or more polyethers are more likely to energetically bind to continuous phase polyol molecules than styrene-acrylonitrile copolymers. The tail of the polyether extends into a continuous phase, which forms a "brush" layer near the particle-fluid interface, shielding the van der Waals force, which is the attractive force between the particles. This phenomenon is known as steric stabilization. In order to form a brush layer that effectively shields Van der Waals forces, some conditions must be met. The tail of the polyether should be similar in chemical composition to the continuous phase so that the tail of the polyether spreads completely into the continuous phase and does not adsorb to the particles. Also, the surface coverage and molecular weight must be high enough so that the brush layer at the interface is thick enough to prevent agglomeration of solid particles.

Large and bulky molecules are known to be effective macromers because particles can be sterically stabilized using a small amount of material. Generally speaking, this means that highly branched polymers have a much larger exclusion volume than linear molecules (eg, monool) and therefore require less branched polymer. Because of the facts. Coupling of polyfunctional polyols with polyisocyanates is also known and has been described in the field of polymeric polyols as a suitable means of increasing the molecular weight of macromers.

Preformed stabilizers (PFS) are known to be useful for preparing polymer polyols with high solid content and lower viscosities. In general, preformed stabilizers include macromers containing reactive unsaturateds (eg, acrylates, methacrylates, maleates, etc.) and monomers (ie, acrylonitrile, styrene, methylmethacrylate, etc.), optionally. Reactions in diluents or solvents (ie, methanol, isopropanol, toluene, ethylbenzene, polyether polyols, etc.) to disperse copolymers (eg, low solids content (eg, less than 20%), or soluble grafts, etc. ) Is an intermediate obtained by producing. Thus, in the process of preforming stabilizers, macromers react with the monomers to form copolymers composed of macromers and monomers. These copolymers, including macromers and monomers, are commonly referred to as forward-formed stabilizers (PFS). The reaction conditions can be controlled so that a portion of the copolymer precipitates from the solution to form a solid. In many applications, dispersions with a low solid content (eg, 3-15% by weight) are obtained. Preferably, the reaction conditions are controlled so that the particle size is reduced, thereby allowing the particles to function as "seeds" in the polymer polyol reaction.

Surprisingly, the dithiocarbonate (or xanthate) group obtained by incorporating carbon disulfide into the molecule during the synthesis of the polyether polyol allows macromers to effectively stabilize the polymer polyol and / or the polymer. It has been found that the amount of reactive unsaturated required for macromers can be reduced or reduced to form preformed stabilizers for polyols.

The present invention relates to macromers having a dithiocarbonate (or xanthate) functional group. These macromers
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) With an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Optionally include reaction products in the presence of at least one catalyst.

The present invention also relates to methods of preparing these macromers. This method
(1) This is a reaction process.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) The polyether dithiocarbonate polyol containing a copolymerization product in the presence of an alkoxylation catalyst.
(B) An ethylenically unsaturated compound having a hydroxyl-reactive group and
(C) Including the reaction step, which optionally reacts in the presence of at least one catalyst.

The present invention also relates to preformed stabilizers. These preformed stabilizers
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) With an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, which comprises a reaction product in the presence of at least one catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) At least one free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, it contains a free radical polymerization product in the presence of a polymer control agent.

The present invention also relates to a method of preparing a preformed stabilizer. This method
(A) Free radical polymerization step
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05 to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) One or more alkylene oxides and
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, optionally comprising a reaction product in the presence of at least one catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) At least one free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, the free radical polymerization step of performing free radical polymerization in the presence of a polymer control agent is included.

The present invention also covers polymeric polyols. The polymer polyol of the present invention
(A) Base polyol and
(B) Below:
(1) A macromer containing a dithiocarbonate functional group.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) One or more alkylene oxides and
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, which optionally comprises a reaction product in the presence of at least one catalyst, and
(2) Preformed stabilizer
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) One or more alkylene oxides and
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, optionally comprising a reaction product in the presence of a catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
A component comprising at least one of the preformed stabilizers, including (4) optionally a liquid diluent, and (5) optionally a free radical polymerization product in the presence of a polymer control agent.
(C) With at least one ethylenically unsaturated monomer,
(D) Free radical polymerization initiator and
(E) optionally comprises an in-situ free radical polymerization product in the presence of a polymer control agent.

The present invention also relates to methods of preparing these polymeric polyols. This method
(I) Free radical polymerization step
(A) Base polyol and
(B) Below:
(1) A macromer having a dithiocarbonate functional group.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) One or more alkylene oxides and
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, which optionally comprises a reaction product in the presence of at least one catalyst, and
(2) Preformed stabilizer
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) One or more alkylene oxides and
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, which optionally comprises a reaction product in the presence of at least one catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) At least one free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, a component containing at least one of the preformed stabilizers, including a free radical polymerization product in the presence of a polymer control agent.
(C) With at least one ethylenically unsaturated monomer,
(D) At least one free radical polymerization initiator and
(E) In some cases, the free radical polymerization step of performing free radical polymerization in the presence of a polymer control agent is included.

The present invention also relates to foams containing these polymeric polyols. These forms
(I) Of the diisocyanate or polyisocyanate component,
(II) With an isocyanate-reactive component containing the above polymer polyol,
(III) Catalyst,
(IV) Foaming agent and
(V) Includes reaction products in the presence of surfactant.

The present invention also relates to a method of preparing a foam. This method
(I) Diisocyanate or polyisocyanate component
(II) With the isocyanate-reactive component containing the above polymer polyol,
(III) Catalyst,
(IV) Foaming agent and
(V) The step of reacting in the presence of a surfactant is included.

Detailed Description of the Invention Next, the present invention will be described for purposes of illustration, not limitation. Except in the examples, or unless otherwise specified, all numerical parameters are prefixed and modified with the term "about" in all cases, and numerical parameters are used to determine the numerical value of the parameter. It should be understood as having the inherent variation characteristics of the underlying measurement technique used. Examples of such numerical parameters include, but are not limited to, OH value, equivalent and / or molecular weight, functional value, amount, percentage, and the like. At a minimum, it does not attempt to limit the application of the doctrine of equivalents to the scope of the claims, and each numerical parameter described herein is a conventional rounding technique, at least in light of the number of significant figures reported. Should be interpreted by applying.

In addition, the numerical range described in the present specification shall include all subranges included in the range described. For example, the range "1-10" shall include the entire subrange between the stated minimum value 1 and the stated maximum value 10 (including the maximum and minimum values), i.e. the minimum value is It is assumed that the value is 1 or more and the maximum value is 10 or less. Unless otherwise specified, all endpoints in the entire range are included. Any maximum limit value described herein shall include all smaller limits contained therein, and any minimum limit value described herein shall be any larger limit value contained therein. Shall include. Accordingly, the Applicant reserves the right to amend the specification, including the claims, and to explicitly state the subranges contained within the scope explicitly stated herein. Since all such ranges are essentially described herein, amending such subranges to be explicitly stated is 35 U.S.A. S. C. Article 112 and 35 U.S. S. C. Meets the requirements of Article 132 (a).

The grammatical articles "a," "an," and "the" used herein are used where "at least one" or "one or more" is specific. Even if it does, it shall include "at least 1" or "1 or more" unless otherwise specified. By way of example, but not by limitation, "a component" means one or more components, and thus potentially more than one component is intended and described. Can be adopted or used to carry out the embodiment. In addition, the use of singular nouns includes the plural, and the use of plural nouns includes the singular, unless the context of use requires otherwise specified.

Equivalents and molecular weights, as indicated by Dalton (Da) herein, are number average equivalents and number average molecular weights, respectively, unless otherwise specified and have been determined by the GPC as described herein.

The number average molecular weight and the weight average molecular weight, respectively, Mn and Mw herein were determined by gel permeation chromatography (GPC) using a method based on DIN 55672-1. The gel permeation chromatography uses a mixed bed column (Agilent PL gel; SDVB; 3 micron pore size: 1 × Mixed-E + 5 micron pore size: 2 × Mixed-D), differential refractometer (RI) detector. Chloroform was used as the eluent and calibrated with polyethylene glycol as the standard sample.

The isocyanate index is the relative stoichiometry of the isocyanate functional groups required to react with the isocyanate-reactive groups present throughout the foam formulation. Expressed as a percentage in this application, therefore, equal stoichiometric amounts of isocyanate functional groups and isocyanate-reactive functional groups in the formulation yield a 100% isocyanate index.

The term "monomer" means a single non-polymerized form of a compound having a relatively low molecular weight, such as acrylonitrile, styrene, methyl methacrylate and the like.

The phrase "polymerizable ethylenically unsaturated monomer" refers to ethylenically unsaturated (> C = C <, that is, two double-bonded carbon atoms) that can undergo an addition polymerization reaction induced by free radicals. It means a monomer containing.

The term preformed stabilizer refers to macromers containing reactive unsaturateds (eg, acrylates, methacrylates, maleates, etc.) with one or more monomers (ie, acrylonitrile, styrene, methyl methacrylate, etc.) and at least one. Dispersions of copolymers (ie, eg, low solids content (eg, less than 30%)), optionally reacted in diluent in the presence of the seed free radical initiator and polymer control agent (PCA). Or as an intermediate obtained by producing (or soluble grafts, etc.).

The term "stability" means the ability of a material to maintain a stable form, eg, the ability to remain in solution or suspension. Polymer polyols with good stability generally also have good filterability.

The phrase "polymer polyol" is used to polymerize one or more ethylenically unsaturated monomers dissolved or dispersed in a polyol in the presence of a free radical catalyst to form a stable dispersion of polymer particles in the polyol. Refers to a composition that can be produced by forming. These polymeric polyols have the beneficial property that, for example, the polyurethane foams and elastomers produced from them exhibit higher load resistance than those provided by the corresponding unmodified polyols.

As used herein, the phrase "polyol feed" refers to a base polyol feed that is present in a polymeric polyol or during the process of preparing a polymeric polyol.

As used herein, the phrase "total feed" refers to the components and / or variations present in each of the various products (ie, preformed stabilizers, polymer polyols, etc.). Refers to the sum of all the amounts of ingredients present in the process of preparing each of the products. The total solids level of the polymer polyol (ie, the weight percent of polyacrylonitrile and polystyrene) was measured by an analytical technique known as near infrared (NIR) spectroscopy. Specific NIR measurements of total solids are described in ASTM D6342-12, "Polyurethane Raw Materials: Determining Hydroxyl Number of Polyols by Near Infrared (NIR). ) Spectroscopy) ”. The modifications used include (1) substitution of absorption bands related to polyacrylonitrile and polystyrene instead of those related to hydroxyl value and (2) acquisition of NIR spectra in reflection mode rather than transmission mode. The use of the reflection mode is due to the polymer polyol being opaque and therefore a scattering material for infrared radiation. Measuring the NIR spectrum in reflection mode reflects more NIR radiation than the PMPO can transmit, resulting in a high quality spectrum for calibration and measurement purposes. The calibration used as a standard was developed according to ASTM D6342-12. In addition, the absorption bands associated with polyacrylonitrile and polystyrene are used to calculate the weight ratio of styrene: acrylonitrile in the total polymer. One of ordinary skill in the art will recognize that this is an analytical confirmation of the main mechanism for controlling the S / AN ratio and is the weight percent of the monomer in the total feed of the reactor.

The hydroxyl or OH value is determined according to ASTM D4274-11, and is reported in mg [KOH] / g [polypoly].

As used herein, "viscosity" is millipascal seconds (mPa.s) measured at 25 ° C. Viscosity was measured at 25 ° C. with an Antonio-Par SVM3000 viscometer. This has been demonstrated to give results comparable to those produced by ASTM-D4878-15. The instrument was calibrated using a mineral oil reference standard of known viscosity.

As used herein, the term dithiocarbonate content refers to the xanthate functionality of a polyether polyol. Xanthate functionality can be involved in the "living polymerization" process.

The dithiocarbonate content was determined by dissolving the sample in deuterated chloroform and running a 400 MHz nuclear magnetic resonance (NMR) (Varian MR400) spectrometer using ^{high resolution 1 H-NMR for characterization.}

The macromer of the present invention is (a) a polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8, and 0.05% by weight to 20% by weight based on the total weight of the polyether polyol. Contains compounds containing the reaction products of the polyether dithiocarbonate polyol having the dithiocarbonate content of.

These polyether dithiocarbonate polyols may have equivalents of about 230 Da or more, or about 280 Da or more, or about 330 Da or more. The equivalent of these polyether polyols may be 5600 Da or less, 5400 Da or less, or 5200 Da or less. These polyether polyols have an equivalent range of any combination, including these upper and lower limits, such as about 230 Da to about 5600 Da, or about 280 Da to about 5400 Da, or about 330 Da to about 5200 Da. obtain.

The functional value of these polyether dithiocarbonate polyols may be about 1 or more, or about 2 or more, or about 3 or more. The functional value of these polyether polyols may also be 8 or less, or 7 or less, or 6 or less. In general, these polyether polyols have functional values in any combination range, including their upper and lower limits, such as about 1 to about 8, or about 2 to about 7, or about 3 to about 6. Can have.

These polyether dithiocarbonate polyols may have a dithiocarbonate content of about 0.05% by weight or more, or about 0.10% by weight or more, or about 0.15% by weight or more. The dithiocarbonate content of these polyether polyols may be 20% by weight or less, 15% by weight or less, or 10% by weight or less. These polyether dithiocarbonate polyols are based on a range of any combination, including these upper and lower limits, for example 100% by weight of the polyether polyols, from about 0.05% to about 20% by weight, or It can have a dithiocarbonate content such as about 0.10% to about 15% by weight, or about 0.15% to about 10% by weight.

These dithiocarbonates, including the polyether polyols, include (i) one or more starter polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8, and (ii) 1 It comprises a copolymerization product of a reaction mixture containing more than one species of alkylene oxide and (iii) carbon disulfide in the presence of an (iv) alkoxylation catalyst.

A suitable starter polyether polyol (i) has an equivalent of 1000 Da or less, or 500 Da or less, or 250 Da or less. The equivalent of the starter polyether polyol is also typically greater than or equal to 30 Da, or greater than or equal to 100 Da, or greater than or equal to 150 Da. Suitable starter-polyether polyols generally have an equivalent range of any combination, including these upper and lower limits, such as 30 Da to 1000 Da, or 100 Da to 500 Da, or 150 Da to 250 Da.

The starter polyether polyol (i) may have an OH value of 56 mgKOH / g polyol or more, 112 mgKOH / g polyol or more, or 220 mgKOH / g polyol or more. These starter polyether polyols may also have an OH value of 1850 mgKOH / g polyol or less, or 560 mgKOH / g polyol or less, or 400 mgKOH / g polyol or less. In general, the starter polyether polyol (i) will be in any combination range, including these upper and lower limits, eg, at least 56 mgKOH / g polyol to 1850 mgKOH / g polyol, or at least 112 mgKOH / g polyol to 560 mgKOH / g. It has an OH value of a polyol, or at least 220 mgKOH / g polyol to 400 mgKOH / g polyol.

The functional value of these starter polyether polyols (i) may be about 1 or more, or about 2 or more, or about 3 or more. The functional value of these starter polyether polyols (i) may also be 8 or less, or 7 or less, or 6 or less. In general, these starter-polyether polyols (i) range from any combination, including their upper and lower limits, eg, about 1 to about 8, or about 2 to about 7, or about 3 to about 6. It may have a functional value such as.

Suitable starter polyether polyols include, for example, polyoxyethylene monool, polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetrol and higher functional polyoxyethylene polyols, polyoxypropylene monool, poly. Includes oxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetrol and higher functional polyoxypropylene polyols, mixtures thereof and the like. When a mixture of alkylene oxides is used, ethylene oxide and propylene oxide are added, for example, simultaneously or sequentially to create an internal block, terminal block or random distribution of oxyethylene and / or oxypropylene groups in the polyether polyol. Can be provided. Suitable starters or initiators for these polyether polyols include, for example, 1-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, etc. Includes ethylenediamine, toluenediamine and the like. Suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like. Alkoxylation of the starter allows the formation of suitable starter polyether polyols. Suitable starter polyether polyols do not have dithiocarbonate groups.

Suitable alkylene oxides for reaction with starter polyether polyols include, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like. In one embodiment of the invention, the alkylene oxide comprises ethylene oxide, propylene oxide and / or a mixture thereof. When used as a mixture, the ethylene oxide content can vary from 2 to 50% by weight of the total oxide feed, as a block, a random co-feed. Alternatively, it can be used as a "cap" to provide high primary hydroxyl containing polyols.

Carbon disulfide also reacts with starter polyether polyols and alkylene oxides in the presence of an alkoxylation catalyst to form a polyether polyol useful as a macromer according to the present invention.

Suitable alkoxylation catalysts (iv) used to obtain polyether dithiocarbonate polyols (a) include basic catalysts (eg, potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.) and composite metal cyanides. Includes catalysts such as catalysts (eg, amorphous and non-amorphous DMC catalysts).

Suitable ethylenically unsaturated compounds with hydroxyl-reactive groups used as component (b) of macromer include, for example, methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate. , 2-Isocyanatoethyl methacrylate, isophorone diisocyanate and 2-hydroxyethyl methacrylate adducts, toluene diisocyanate and 2-hydroxypropyl acrylate adducts and the like.

As used herein, the catalyst (c) suitable for macromer includes virtually any catalyst known to be suitable for urethane reactions that can be used as component (c) in the present invention. Suitable polyurethane catalysts are well known in the art. An extensive list is set forth in US Pat. No. 5,011,908, the disclosure of which is incorporated herein by reference. Suitable organotin catalysts include tin salts of carboxylic acids and dialkyl tin salts. Examples include stannous octanoate, dibutyltin dilaurate, dibutyltin diacetate, stannous oleate and the like. The catalyst also includes bismuth (III) neodecanoate and the like.

In the process of preparing the macromer, the polyether dithiocarbonate polyol (a) is typically an ethylenically unsaturated compound (b), optionally with a hydroxyl-reactive group, and optionally at least one catalyst (. In the presence of c), the reaction is carried out at a temperature of about 25 ° C. to about 250 ° C. for a period of about 1 hour to about 10 hours. This reaction is preferably carried out at a temperature of about 60 ° C. to about 200 ° C. for a time of about 2 hours to about 7 hours.

In the present specification, the preformed stabilizers are (1) macromers described herein, (2) at least one ethylenically unsaturated monomer, and (3) at least one free radical polymerization. It comprises an initiator and optionally (4) a liquid diluent and optionally (5) a free radical polymerization product in the presence of a polymer control agent.

Macromer (1) is as described herein with respect to the preformed stabilizers according to the invention and the methods for producing them. In one embodiment, macromer (1) is a polyether dithiocarbonate polyol having (a) a functional value of equivalents 1-8 of 230 Da-5600 Da and a dithiocarbonate content of 0.05-20 wt%. i) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8, (ii) alkylene oxide and (iii) carbon disulfide. The reaction mixture containing (iv) a polyether dithiocarbonate polyol containing a copolymerization product in the presence of an alkoxylation catalyst, (b) optionally an ethylenically unsaturated compound having a hydroxyl-reactive group, and (c). ) In some cases, it may be included in the presence of a catalyst.

In one embodiment, suitable ethylenically unsaturated compounds having a hydroxyl-reactive group for (b) in macromer (1) are methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-. Includes compounds selected from the group consisting of adducts such as dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, isophorone diisocyanate and 2-hydroxyethyl methacrylate, toluene diisocyanate and 2-hydroxypropyl acrylate adducts and the like.

Ethylene unsaturated monomers (2) suitable for the preformed stabilizers of the present invention include, for example, aliphatic conjugated dienes (eg, butadiene and isoprene); monovinylidene aromatic monomers (eg, styrene, α- Methylstyrene, (t-butyl) styrene, chlorostyrene, cyanostyrene and bromostyrene, etc.); α, β-ethylenically unsaturated carboxylic acids and esters thereof (eg acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2 -Hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleic anhydride, etc.); α, β-ethylenically unsaturated nitriles and amides (eg, acrylonitrile, methacrylonitrile, acrylamide, methacrylicamide, N, N-dimethylacrylamide, N -(Dimethylaminomethyl) acrylamide, etc.); Vinyl esters (eg, vinyl acetate, etc.); Vinyl ethers, vinyl ketones, vinyl halides and vinylidene, and a wide variety of others that can be copolymerized with the above-mentioned monomer adducts or reactive monomers. Includes ethylenically unsaturated materials. It is understood that a mixture of two or more of the above-mentioned monomers is also suitable for use in the production of preformed stabilizers. Among the above monomers, monovinylidene aromatic monomers, particularly styrene, and ethylenically unsaturated nitriles, particularly acrylonitrile, are preferable.

When using a mixture of monomers, it is preferable to use a mixture of two types of monomers. These monomers are typically in a weight ratio of 80:20 (styrene: acrylonitrile) to 20:80 (S: AN), or 75:25 (S: AN) to 25:75 (S: AN). used.

Suitable free radical polymerization initiators (3) for preformed stabilizers include, for example, peroxides (eg, alkyl hydroperoxides and aryl hydroperoxides, alkyl peroxides and aryl peroxides, etc.), peresters, persulfates. , Perborates, peroxides, azo compounds and the like. Some specific examples are hydrogen peroxide, di (t-butyl) -peroxide, t-butylperoxydiethyl acetate, t-butylperoctate, t-butylperoxyisobutyrate, 1,1-di (t). -Butylperoxy) cyclohexane, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperbenzoate, t-butylperoxypivarate, t-amylperoxypivalate, t-butylperoxy-2-ethylhexa Noate, 1,1-di (t-amylperoxy) cyclohexane, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobis (isobutyronitrile), 2,2'-azobis- (2-methylbutyro) Examples include catalysts such as nitrile).

Suitable catalyst concentrations are based on the total weight of the components (ie, 100% by weight of the total weight of the macromer, ethylenically unsaturated monomer, free radical polymerization initiator, and optionally the liquid diluent and / or chain transfer agent). Based on this, it ranges from about 0.01 to about 2% by weight, or about 0.05 to 1% by weight, or 0.05 to 0.3% by weight.

Diluents (4) suitable for the preformed stabilizers of the present invention include, for example, compounds such as monools (ie, monohydroxyalcohols), polyols, hydrocarbons, ethers and the like, and mixtures thereof. .. Suitable monools include all alcohols containing at least one carbon atom, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec. Includes-butanol, tert-butanol, n-pentanol, 2-pentanol, 3-pentanol and the like, and mixtures thereof. The preferred monool is isopropanol.

Suitable polyols used as diluent (4) include, for example, poly (oxypropylene) glycol, poly (oxypropylene) triol and higher functional poly (oxypropylene) polyols. Such polyols include poly (oxypropylene-oxyethylene) polyols. However, preferably, the oxyethylene content should constitute less than about 50%, preferably less than about 30% of the total. Ethylene oxide can be incorporated in any form along the polymer chain. In other words, ethylene oxide can be incorporated into the inner block, incorporated as the outer block, or randomly distributed along the polymer chain. It is well known in the art that polyols have varying amounts of non-induced unsaturation. The degree of unsaturated does not adversely affect the formation of polymer polyols according to the present invention.

For the purposes of the present invention, useful polyols should have a number average molecular weight of about 400 Da or greater, and the number averages used herein are values derived from theoretical hydroxyl values. The true number average molecular weight may be slightly smaller depending on the extent to which the functional value of the true molecule falls below the starting or theoretical functional value.

The polyols used can have a wide range of hydroxyl values. Generally, the hydroxyl value of the polyol used in the present invention ranges from about 20 mg KOH / g polyol and below to about 280 mg KOH / g polyol and above (from about 20 mg KOH / g polyol and lower, to about 280 mg KOH). / g polyol and higher) can be in the range. The hydroxyl value is defined as the number of milligrams of potassium hydroxide required for complete hydrolysis of a fully phthalated derivative prepared from 1 gram of polyol. The hydroxyl value is the equation:
OH = (56.1 × 1000 × f) / m. w.
[During the ceremony:
OH = hydroxyl value of polyol;
f = functional value, i.e., average hydroxyl value per molecule of polyol; and
m. w. = Molecular weight of polyol]
It can be defined by.

The very polyol used depends on the end use of the polyurethane product being manufactured. The molecular weight or hydroxyl value is appropriately selected to provide the desired foam processing and / or physical properties when the polymeric polyol produced from the polyol is converted to polyurethane. The polyol preferably has a hydroxyl value of about 50 mgKOH / g polyol to about 150 mgKOH / g polyol in the case of semi-soft foam, and a hydroxyl value of about 25 mgKOH / g polyol to about 70 mgKOH / g polyol in the case of soft foam. Have. Such limitations are not intended to be limiting and are merely exemplary of the many possible combinations of the polyol copolymers described above.

Preferred polyol components used as diluents in the present invention typically include suitable starter materials having, for example, 4 or more hydroxyl groups (eg, pentaerythritol, sorbitol, sorbitol diether, mannitol, mannitol diether). , Arabitol, diether of arabitol, sucrose, oligomers of polyvinyl alcohol or glycidol, mixtures thereof, etc.) alkylene oxide adducts.

When using a mixture of monool and polyol as the diluent for the preformed stabilizer, the polyol preferably constitutes only a small amount of the diluent and the monool constitutes the major amount. In general, polyols make up less than 30 weight percent, preferably less than about 20 weight percent, and most preferably less than about 15 weight percent of diluent. The amount of polyol component present in the diluent is less than the concentration at which gelation occurs in the preformed stabilizer.

Generally, the amount of diluent is less than 40% by weight, based on 100% by weight of PFS (preformed stabilizer).

The polymer control agent (5) may also be present in the preformed stabilizers of the present invention and in the process of producing the preformed stabilizers. Suitable polymer control agents for this aspect of the invention include, for example, isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride. included. Polymer control agents are also commonly referred to as molecular weight modifiers. These compounds are used in conventional amounts to control the molecular weight of the copolymer.

Suitable processes for preparing preformed stabilizers are known methods described, for example, in US Pat. Nos. 5,196,476, 5,268,418, and 7,759,423. Similar to, and their disclosure is incorporated herein by reference. In general, the process of preparing a preformed stabilizer is similar to the process of preparing a polymer polyol. The temperature range is not important and can vary from about 80 ° C to about 150 ° C or higher, preferably about 115 ° C to about 125 ° C. The catalyst and temperature should be selected so that the catalyst has a reasonable rate of decomposition relative to the residence time in the reactor of the continuous flow reactor or the supply time of the semi-batch reactor.

The mixing conditions used in this process are obtained using a back mixed reactor (eg, a stirring flask or a stirring autoclave). This type of reactor keeps the reaction mixture relatively uniform, thus preventing local high ratios of monomers to macromers. Locally high ratios of monomers to macromers occur, such as in tubular reactors, when all of the monomers are added to the first part of the reactor. In addition, more efficient mixing can be achieved by using an external pump around loop outside the reactor section. For example, to facilitate internal mixing of the components, the contents flowing through the reactor may be removed from the bottom of the reactor via external piping and returned to the top of the reactor (or vice versa). This external loop may include a heat exchanger if desired.

The combination of conditions selected for the preparation of preformed stabilizers must not cause cross-linking or gel formation of the preformed stabilizers, which are used in preparing the polymeric polyol composition. It may adversely affect the performance of the final product. Combinations where the diluent concentration is too low, the precursor and / or monomer concentration is too high, the catalyst concentration is too high, the reaction time is too long, and the precursor is too unsaturated are preserved by cross-linking or gelation. The effect of the stabilizer formed may be lost.

Particularly preferred processes for preparing preformed stabilizers herein are those described, for example, in US Pat. No. 5,196,476 and US Pat. No. 5,268,418, which are described herein. The disclosure is incorporated herein by reference. Preferred diluents and relative concentrations, ethylenically unsaturated monomers and relative concentrations, free radical initiators and relative concentrations and process conditions are described in US Pat. Nos. 5,196,476, 5,268,418 and US Pat. It is described in Pat. No. 7,759,423.

It is clear that the macromers of the present invention differ from the macromers described by these references and therefore result in structurally different preformed stabilizers.

The polymeric polyols of the present invention were selected from the group consisting of (A) base polyols, (B) (1) macromers described herein and (2) preformed stabilizers described herein. In-situ free radicals in the presence of (C) at least one free radical initiator and, optionally, a polymer regulator, of the component and one or more ethylenically unsaturated monomers. The process for the preparation of polymer polyols, including polymerization products, involves free radical polymerization of these components. The obtained polymer polyol shows a high solid content, i.e. 20 to 70% by weight based on the total weight of the obtained polymer polyol. Generally, the solid content of the polymer polyol may typically be about 20% by weight or more, or about 30% by weight or more, or about 40% by weight or more. Generally, the solid content of the polymer polyol will also typically be about 70% by weight or less, or about 60% by weight or less, or about 55% by weight or less. Generally, these polymeric polyols are solids in any combination range, including these upper and lower limits, such as 20-70% by weight, or about 30-60% by weight, or about 40-55% by weight. It can have a content content. These polymeric polyols also have good viscosities, ie from about 1000 to about 15,000 mPa. s is shown. Generally, these polymer polyols are about 1000 mPa. s or more, or about 4000 mPa. It may have a viscosity of s or more. Polymer polyols are also about 15,000 mPa. s or less, or about 10,000 mPa. It may have a viscosity of s or less. In general, polymer polyols range from any combination, including these upper and lower limits, eg, 1000-15,000 mPa. s, or 4,000 to 10,000 mPa. It may have a viscosity such as s. The polymeric polyols of the present invention also typically have good filterability.

The base polyol (A) suitable for this aspect of the present invention includes, for example, a base polyol such as a polyether polyol. Suitable polyether polyols include those having a functional value of about 2 or more, or about 3 or more. Suitable polyether polyols have a functional value of about 8 or less, or about 6 or less. Suitable polyether polyols may also have a range of any combination, including these upper and lower limits, such as at least about 2 to about 8, or at least about 3 to about 6. The OH value of a suitable polyether polyol is about 10 mgKOH / g polyol or more, preferably about 15 mgKOH / g polyol or more, and most preferably about 20 mgKOH / g polyol or more. Polyether polyols also typically have an OH value of about 180 mgKOH / g polyol or less, preferably about 100 mgKOH / g polyol or less, most preferably about 70 mgKOH / g polyol or less. Suitable polyether polyols are in any combination range, including these upper and lower limits, eg, 10 mgKOH / g polyols to about 180 mgKOH / g polyols, or about 15 mgKOH / g polyols to about 100 mgKOH / g polyols, or It may have an OH value such as about 20 mgKOH / g polyol to about 70 mgKOH / g polyol. The (number average) molecular weight of a suitable polyether polyol is typically greater than or equal to about 600 Da, or greater than or equal to about 2,000 Da, or greater than or equal to about 3,000 Da. Polyether polyols typically have a (number average) molecular weight of 15,000 Da or less, or 12,000 Da or less, or 8,000 Da or less. Suitable polyether polyols also have a (number average) molecular weight in any combination range, including these upper and lower limits, eg, about 600 Da to about 15,000 Da, or about 2000 Da to about 12,000 Da, or It can have from about 3000 Da to about 8000 Da or less.

Examples of such compounds include polyoxyethylene glycol, polyoxyethylene triol, polyoxyethylene tetrol and higher functional polyoxyethylene polyols, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetrol and Examples thereof include polyoxypropylene polyols having higher functional values and mixtures thereof. When a mixture is used, ethylene oxide and propylene oxide can be added simultaneously or sequentially to provide an internal block, terminal block or random distribution of oxypropylene and / or oxyethylene groups in the polyether polyol. .. Suitable starters or initiators for these compounds include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine and the like. included. Alkoxylation of the starter allows the formation of suitable polyether polyols for the base polyol component.

Other suitable base polyols of the invention include alkylene oxide adducts of non-reducing sugars and sugar derivatives, alkylene oxide adducts of phosphorous and polyphosphorous acids, alkylene oxide adducts of polyphenols, natural oils (eg, for example. Includes polyols prepared from (such as castor oil) and alkylene oxide adducts of polyhydroxyalkanes other than those listed above.

Exemplary alkylene oxide adducts of polyhydroxyalkanes include, for example, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-dihydroxyhexane, 1,5-dihydroxyhexane. -And 1,6-dihydroxyhexane, 1,2-dihydroxyoctant, 1,3-dihydroxyoctant, 1,4-dihydroxyoctant, 1,6-dihydroxyoctant and 1,8-dihydroxyoctant, 1,10-dihydroxydecane , Glycerol, 1,2,4-tirhydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylol ethane, 1,1,1-trimethylol Includes alkylene oxide adducts such as propane, pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, sorbitol, mannitol.

Other polyols that can be used include alkylene oxide adducts of non-reducing sugars, where the alkoxide has 2-4 carbon atoms. Non-reducing sugars and sugar derivatives include sucrose, alkyl glycosides (eg, methyl glycosides, ethyl glucosides, etc.), glycol glucosides (eg, ethylene glucosides, propylene glycol glucosides, glycerol glucosides, 1,2,6-hexanetriol glucosides). Etc.), as well as alkylene oxide adducts of alkyl glycosides disclosed in US Pat. No. 3,073,788 (this disclosure is incorporated herein by reference).

Other suitable polyols include polyphenols and preferably their alkylene oxide adducts, where the alkylene oxide has 2-4 carbon atoms. Among the suitable polyphenols are, for example, bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, novolak resins, condensation products of various phenolic compounds and achlorein (eg, 1,1,3-tris). (Hydroxyphenyl) propane), condensation products of various phenolic compounds with glyoxal, glutaaldehyde, and other dialdehydes (eg, 1,1,2,2-tetrakis (hydroxyphenol) ethane) and the like.

Phosphorous acid and polyphosphoric acid alkylene oxide adducts are also useful polyols. These include ethylene oxide, 1,2-epoxy-propane, epoxybutane, 3-chloro-1,2-epoxypropane and the like as preferred alkylene oxides. Phosphoric acid, phosphorous acid, polyphosphoric acid (eg, tripolyphosphoric acid, etc.), polymethaphosphoric acid, etc. are preferred for use herein.

The component suitable for (B) is selected from the group consisting of the macromer (1) described herein and the preformed stabilizer (2) described herein.

The polymeric polyols of the present invention and the ethylenically unsaturated monomers (C) suitable for methods of preparing them include the ethylenically unsaturated monomers described above with respect to the preparation of preformed stabilizers. Other suitable monomers include, for example, aliphatic conjugated dienes (eg, butadiene and isoprene); monovinylidene aromatic monomers (eg, styrene, α-methyl-styrene, (t-butyl) styrene, chlorostyrene, cyano). Styrene, bromostyrene, etc.); α, β-ethylenically unsaturated carboxylic acids and their esters (eg acrylic acid, methacrylate, methyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleine anhydride Acids, etc.); α, β-ethylene unsaturated nitriles and α, β-ethylene unsaturated nitrile amides (eg, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N-dimethylacrylamide, N- (dimethylamino) (Methyl) acrylamide, etc.); Vinyl esters (eg, vinyl acetate, etc.); Vinyl ethers, vinyl ketones, vinyl chloride and vinylidene chloride, and a wide variety of other ethylenic properties that can be copolymerized with the above-mentioned monomer adducts or reactive monomers. Includes unsaturated materials. Mixtures of two or more of the aforementioned monomers are also understood to be suitable for use in the manufacture of preformed stabilizers. Among the above monomers, monovinylidene aromatic monomers, particularly styrene, and ethylenically unsaturated nitriles, particularly acrylonitrile, are preferable. According to this aspect of the invention, these ethylenically unsaturated monomers preferably contain styrene and its derivatives, acrylonitrile, methyl acrylate, methyl methacrylate, vinylidene chloride, as well as the particularly preferred monomers styrene and acrylonitrile.

Styrene and acrylonitrile may be used in sufficient amounts so that the weight ratio of styrene to acrylonitrile (S: AN) is about 80:20 to 20:80, more preferably about 75:25 to 25:75. preferable. These ratios are suitable for polymer polyols and the process of preparing them, regardless of whether the polymer polyols contain the ethylenically unsaturated macromers or preformed stabilizers of the invention.

Overall, the amount of one or more ethylenically unsaturated monomers present in the preformed stabilizer-containing polymer polyol is about 20% by weight or more, based on 100% by weight of the polymer polyol. In one embodiment, the solid content is from about 20 to about 70% by weight. Typically, the solids content of the preformed stabilizer-containing polymer polyol ranges from any combination range, including these upper and lower limits, eg, about 20 to about 70% by weight, or about 30 to about 30. It may be in the range of about 60% by weight, or about 40 to about 55% by weight.

Overall, the amount of ethylenically unsaturated monomers present in the polymer polyol containing the macromer of the present invention is about 20% by weight or more, based on 100% by weight of the polymer polyol. In one embodiment, the solid content is in the range of about 20 to about 70% by weight.

Suitable free radical initiators include those described above with respect to the preparation of preformed stabilizers. Some useful initiators have a sufficient half-life within the temperature range used to form the stabilizer (ie, the half-life is less than about 25% of the residence time in the reactor at any given time. There should be a catalyst with). Preferred initiators for this portion of the invention include acyl peroxides (eg, didecanoyl peroxide and dilauroyl peroxide), alkyl peroxides (eg, t-butylperoxy-2-ethylhexanoate, 1,1-di). (T-butylperoxy) cyclohexane, 1,1-di (t-amylperoxy) cyclohexane, t-butylperoxypivalate, t-amylperoctate, t-amylperoxypivalate, 2,5-dimethyl-hexane- 2,5-Di-per-2-ethylhexoate, t-butylperneodecanoate, t-butylperbenzoate and 1,1-dimethyl-3-hydroxybutylperoxy-2-ethylhexanoate, etc.) , And azo catalysts (eg, azobis (isobutyronitrile), 2,2'-azobis- (2-methoxylbutyronitrile), etc.), and mixtures thereof. The above acyl peroxide and azo catalysts are most preferred.

The amount of initiator used herein is not critical and can vary over a wide range. Generally, the amount of initiator is in the range of about 0.01-2% by weight, based on 100% by weight of the final polymer polyol. An increase in the catalyst concentration results in an increase in the monomer conversion rate up to a certain point, but beyond this, a further increase does not result in a substantial increase in the conversion rate. The particular catalyst concentration selected will usually be optimal, taking into account all factors, including cost.

Suitable polymer control agents include, for example, one or more monools (eg, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec.-Butanol, which are usually alcohols having at least one carbon atom. , T-butanol, n-pentanol, 2-pentanol, 3-pentanol, allyl alcohol, etc.) and mixtures thereof. The preferred monool is isopropanol. Other known polymer regulators include compounds such as, for example, ethylbenzene and toluene. According to the present invention, the most preferred polymer control agents include isopropanol, ethanol, tert-butanol, toluene, ethylbenzene and the like.

The polymer control agent may be used in substantially pure form (ie, as is commercially available), or may be recovered in crude form from the polymer polyol process and reused as is. For example, if the polymer control agent is isopropanol, it can be recovered from the polymer polyol process and a subsequent product campaign in the presence of isopropanol (ie, US Pat. No. 7,179, It can be used at any time of 882 (such as the manufacture of PFS A and PFS B in Table 1 of No. 882, the disclosure of which is incorporated herein by reference). The amount of crude polymer control agent in the total polymer control agent may range from 0% to 100% by weight.

Polymer polyols containing preformed stabilizers of the invention are described, for example, in US Pat. Nos. 4,148,840, 4,242,249, 4,954,561, 4,745,153. , No. 5,494,957, No. 5,990,185, No. 6,455,603, No. 4,327,005, No. 4,334,049, No. 4,997,857, No. 5,196,476, 5,268,418, 5,854,386, 5,990,232, 6,013,731, 5,554,662, 5,5 It is prepared by utilizing the processes disclosed in 594,066, 5,814,699 and 5,854,358 (these disclosures are incorporated herein by reference). As described in them, the ratio of monomer to polyol is kept low throughout the reaction mixture during the process. This is achieved by adopting conditions that provide rapid conversion from monomer to polymer. In practice, by controlling the temperature and mixing conditions for semi-batch and continuous operation, and by slowly adding the monomer to the polyol for semi-batch operation, the ratio of monomer to polyol is kept low.

In the process of preparing the polymer polyol, the temperature range is not important and can vary from about 100 ° C to about 140 ° C, or perhaps even higher, with a preferred range of 115 ° C to 125 ° C. As described herein, the catalyst and temperature are selected so that the catalyst has a reasonable rate of decomposition relative to the residence time in the reactor of the continuous flow reactor or the supply time of the semi-batch reactor. Should be.

The mixing conditions used are those obtained using a back-mixer (eg, a stirring flask or a stirring autoclave). This type of reactor keeps the reaction mixture relatively uniform, thus preventing local high ratios of monomers to macromers. Locally high ratios of monomers to macromers occur, such as in tubular reactors, when such reactors are operated so that all of the monomers are added to the first part of the reactor. In addition, more efficient mixing can be achieved by using an external pump-around loop over the reactor area. For example, to facilitate internal mixing of the components, the contents flowing through the reactor may be removed from the bottom of the reactor via external piping and returned to the top of the reactor (or vice versa). This external loop may include a heat exchanger if desired.

Utilization of the processes described in US Pat. Nos. 5,196,476 and 5,268,418 is preferred in this aspect of the invention. This is because they allow the preparation of polymer polyols with a wide range of monomer compositions, polymer contents and polymer polyols that could not be otherwise prepared with the required required stability. However, whether the use of the processes disclosed in US Pat. Nos. 5,916,476 and 5,268,418 is essential is satisfactory without the process parameters using any of these processes. It depends on whether the polymer polyol can be prepared.

The polymer polyol of the present invention contains a dispersion, in which the size of the polymer particles, which are either individual particles or aggregates of individual particles, is relatively small, which is a preferred embodiment. All are substantially less than about 1-3 microns. However, when those with a high styrene content are used, the particles tend to be large. However, the resulting polymeric polyol is more useful, especially when the end application requires as little scorch as possible. In a preferred embodiment, substantially all products (ie, about 99% or more) pass through the filters used in the filtration failure (filterability) tests described in connection with the Examples. This requires the use of filters where polymer polyol products cannot tolerate large quantities of relatively large particles of all types of relatively advanced mechanical systems currently used in the mass production of polyurethane products. It is guaranteed that it can be processed effectively with (using impact type mixing). For less rigorous applications, about 50% of the product will be satisfied if it passes through the filter. Depending on the application, it is satisfied that the product is useful even when only about 20% or less passes through the filter. Therefore, the polymeric polyols of the present invention preferably contemplate products in which only 20%, preferably 50% or more, and most preferably 95% or more pass through the filter.

According to the present invention, the stabilizer is present in sufficient amount to ensure that satisfactory stabilization results in the desired filtration failure, centrifugable solids level and viscosity. In this regard, the amount of preformed stabilizer is generally in the range of about 1 to about 20% by weight, based on the total supply. Generally, the amount of preformed stabilizer is about 1 to about 20% by weight, about 2 to about 15 based on the range of any combination, including these upper and lower limits, eg, total supply. It can be in the range such as% by weight. As one of ordinary skill in the art knows and understands, various factors such as free radical initiator, solids, S: AN weight ratio, process conditions, etc. affect the optimum amount of preformed stabilizer. give.

If it is desirable not to use preformed stabilizers, macromers can be utilized in the polymer polyol process at any level of 0.5% to 30% based on the total weight of the polymer polyol. Macromer is typically used in polymer polyol processes in an amount of about 0.5% by weight or more, or about 1% by weight or more, or about 2% by weight or more. Macromers are also typically used in polymer polyol processes in an amount of about 30% by weight or less, or about 20% by weight or less, or about 15% by weight or less. Generally, the amount of macromer used in the polymer polyol process ranges from any combination range, including these upper and lower limits, eg, about 0.5% to about 30% by weight, or about 1% by weight. It can range from about 20% by weight, or from about 2% to about 15% by weight.

Polyurethanes containing in-situ polymer polyols, preferably polyurethane foams and methods for producing these polymeric polyols are also part of the present invention. The in-situ polymer polyols suitable for these polyurethanes may be either directly prepared from the macromers of the invention or prepared from preformed stabilizers based on the macromers of the invention. These polyurethanes contain a reaction product of a polyisocyanate component or a prepolymer thereof and an isocyanate-reactive component containing the polymer polyol of the present invention. The process of preparing these polyurethanes comprises reacting the polyisocyanate component or its prepolymer with an isocyanate-reactive component containing the polymer polyol of the present invention.

In another aspect of the invention, the flexible polyurethane foam is one or more catalysts of the polyisocyanate component with an isocyanate-reactive component of the polyisocyanate component, including the novel in-situ polymer polyol described herein. Includes one or more foaming agents and, optionally, reaction products in the presence of one or more surfactants. In addition, the isocyanate-reactive component may further comprise one or more cross-linking agents, one or more chain extenders, and / or one or more polyether polyols with high ethylene oxide content. It is also possible that the isocyanate-reactive component further comprises one or more polyoxyalkylene polyols, polyether polyols, polyester polyols, polycarbonate ether polyols, polythioethers, polycarbonates, polyacetals and the like, and mixtures thereof. Various additives and / or auxiliaries known to be useful in the preparation of foam may also be present.

The method for preparing the flexible polyurethane foam is as follows: (I) a polyisocyanate component, (II) an isocyanate-reactive component containing the novel polymer polyol described herein, (III) one or more catalysts, and (IV) 1 Includes reacting in the presence of one or more foaming agents and, optionally, one or more surfactants. In addition, cross-linking agents, chain extenders, other isocyanate-reactive components, etc., as described herein, as well as various other additives and auxiliaries may also be present.

(I) Polyisocyanates suitable for the polyisocyanate component include those known in the art to be suitable for the preparation of flexible polyurethane foams. The polyisocyanate may be bifunctional or polyfunctional, for example, (cyclo) aliphatic diisocyanate and / or (cyclo) aliphatic polyisocyanate, aromatic diisocyanate and / or aromatic polyisocyanate, and aromatic fat. Includes group diisocyanates and / or aromatic aliphatic polyisocyanates. Some specific examples of suitable aromatic polyisocyanates and aromatic diisocyanates include compounds such as toluene diisocyanates, diphenylmethane diisocyanates, polymethylene polyphenyl polyisocyanates and mixtures or blends thereof.

In the present specification, as the isocyanate-reactive component which is the component (II), a suitable compound used for the preparation of a flexible polyurethane foam is a polymer polyol formed of the novel in-situ described herein. including. According to the present invention, the isocyanate-reactive component (II) is a conventional (ie, non-solid-containing) isocyanate-reactive component (eg, polyoxyalkylene polyol, polyether polyol, polyester polyol, polythioether, polyacetal, polycarbonate). , Polycarbonate ether polyol, etc., and mixtures thereof, etc.) may be additionally included. These isocyanate-reactive compounds have a functional value of 2-8, or 2-6, or 2-4, and have a functional value of 1000 Da to 12,000 Da, or 1000 Da to 8,000 Da, or 2000 Da to 6000 Da. It has a molecular weight (number average). In addition, low molecular weight isocyanate-reactive components such as cross-linking agents and / or chain extenders can be used. These low molecular weight isocyanate-reactive components may have a functional value of 2 and a (number average) molecular weight in the range of 61 Da to 500 Da; a functional value of 3 to 4 and 92 Da to less than 1000 Da, or 92 Da. Includes cross-linking agents that may have a (number average) molecular weight in the range from to 750 Da or less. Examples of suitable chain extenders are ethylene glycol, 2-methyl-1,3-propanediol, 1,2-propanediol and 1,3-propanediol, 1,3-butanediol and 1,4-butanediol. And their mixtures such as 2,3-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and their alkylene oxide adducts. Some examples of suitable cross-linking agents include mixtures thereof such as glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine, and alkylene oxide adducts thereof. It is also possible to use a polyether polyol having a high ethylene oxide content.

At least one polyurethane catalyst is required to catalyze the reaction of monool, polyol and water with polyisocyanates. It is common to use organic amines and / or organotin compounds for this purpose. Suitable polyurethane catalysts are well known in the art. An extensive list is set forth in US Pat. No. 5,011,908, the disclosure of which is incorporated herein by reference. Suitable organotin catalysts include tin salts of carboxylic acids and dialkyl tin salts. Examples include first tin octoart, dibutyltin dilaurate, dibutyltin diacetate, first tin oleate and the like. Suitable organic amine catalysts are tertiary amines such as trimethylamine, triethylamine, triethylenediamine, bis (2,2'-dimethylamino) ethyl ether, N-ethylmorpholine, diethylenetriamine and the like. Preferred catalysts are amine catalysts such as bis (dimethylaminoethyl) ether in dipropylene glycol and triethylenediamine in dipropylene glycol. These are commercially available as Niax A-1 and Niax A-33, respectively.

Polyurethane catalysts are typically used in amounts ranging from about 0.05 to about 3 parts, or about 0.1 to about 2 parts per 100 parts of the isocyanate-reactive mixture.

Foaming agents (III) suitable for the present invention include, for example, chemical foaming agents and / or physical foaming agents. Some examples of foaming agents suitable for the present invention are water, formic acid, carbon dioxide, chlorofluorocarbons, highly fluorinated and / or hyperfluorinated hydrocarbons, chlorinated hydrocarbons, aliphatics and / or fats. Cyclic hydrocarbons (eg, propane, butane, pentane, hexane, etc.), or acetals (eg, methylal, etc.) can be mentioned. In the present invention, it is possible to use a mixture of foaming agents. If a physical foaming agent is used, it is typically added to the isocyanate-reactive component of the system. However, they may also be added in the polyisocyanate component or in a combination of both the isocyanate-reactive component and the polyisocyanate component. The foaming agent may also be used in the form of an emulsion of isocyanate-reactive components. In the present specification, a combination of water and one or more auxiliary foaming agents is also suitable. In addition, water may be used as the only foaming agent.

The amount of foaming agent or mixture of foaming agents used is 0.5 based on the range of any combination, including these upper and lower limits, eg, the total weight of component (B) in each case. It can be in the range of ~ 20% by weight, or 0.75-10% by weight. When water is a foaming agent, it is typically present in an amount of 0.5-10% by weight, or 0.75-7% by weight, based on the total weight of component (B). The addition of water can be achieved in combination with the use of the other foaming agents described above.

Preferably, a surfactant is used to prepare the foam. Surfactants are known to help stabilize the foam until it hardens. Surfactants suitable for the present invention are well known in the polyurethane industry. A wide variety of organosilicone surfactants are commercially available. Examples of suitable surfactants include DC-5043, DC-5164 and DC-5169, and Tegostab B8244, a product of Momentive Performance Materials' products Niax L-620 and Evonik-Goldschmidt. Many other silicone surfactants known to those of skill in the art can be used in place of these suitable silicones. The amount of surfactant can be in any combination range, including upper and lower limits, such as about 0.1-4 parts per 100 parts of isocyanate-reactive mixture, or about 0.2-3 parts. possible.

Other optional ingredients that may be present in the soft foam formulation include, for example, flame retardants, antioxidants, pigments, dyes, liquid fillers and solid fillers. Such commercially available additives, when used, are included in the foam in conventional amounts.

Soft foams are prepared using methods well known in the industry. These methods may include continuous or discontinuous free-rise slabstock foam process and molded foam process. In a typical slabstock process, isocyanates move through a mixing head to a trough, where they are continuously mixed with other compounded chemicals and overflow onto a mobile conveyor. Alternatively, the reaction mixture is deposited directly on the mobile conveyor. In another embodiment, high pressure liquid carbon dioxide is fed to one or more blending components, typically polyols, into a mixing head, and the resin blend passes through a reduced pressure foaming device, resulting in The resulting bubbles are deposited on the conveyor. The foam expands and swells as it moves down the conveyor, forming a continuous foam slab. The slab is cut into blocks or buns of the desired length for curing and storage. After curing for 1 day or longer, these foam buns can be cut into the desired shape for end use. In a discontinuous process, the reactants are mixed quickly in the head or in a large mixing chamber. The reaction mixture is then placed in a large box or other suitable container, where expansion of the foam occurs, forming a bun with the lateral dimensions of the container.

A typical mold forming foam process is usually a one-shot approach in which a specific amount of isocyanate flow (“A” side) is quickly combined and mixed with a specific amount of the remaining compounding component (“B” side). Is adopted. An additional stream can be used to incorporate one or more specific components not included in the "B" side stream. The mixture is immediately placed in the mold and then closed. The foam expands to fill the mold, producing parts with the shape and dimensions of the mold.

According to the present invention, the soft foam is prepared with an isocyanate index in the range of 70-130, or 80-120, or 90-110. The term "isocyanate index" is sometimes referred to as the NCO index and is defined herein as the ratio of reactive isocyanate groups (equivalents) to active hydrogen groups (equivalents) multiplied by 100%.

Although less preferred, a prepolymer approach for producing foam is also available. In this approach, a significant portion of the isocyanate-reactive mixture reacts with the polyisocyanate, and then the resulting prepolymer reacts with the remaining components.

In the first aspect, the present invention is a macromer.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Target the macromer, optionally comprising a reaction product in the presence of a catalyst.

In a second aspect, the present invention comprises the polyether dithiocarbonate polyol (a) having an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, and a dithiocarbonate content of 0.10 to 15% by weight. In addition, in the reaction product contained in the polyether dithiocarbonate polyol (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and 2 to 7. The macromer of the first embodiment having a functional value, wherein the alkylene oxide (ii) contains ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) contains a composite metal cyanide complex catalyst. To do.

In a third aspect, in the present invention, the ethylenically unsaturated compound (b) having a hydroxyl-reactive group is methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. For macromers of the first or second embodiment, comprising 2-isocyanatoethyl methacrylate, isophorone diisocyanate and 2-hydroxyethyl methacrylate additives, toluene diisocyanate and 2-hydroxypropyl acrylate additives, or mixtures thereof. To do.

In a fourth aspect, the present invention is directed to the macromer of any of the first to third aspects, wherein the catalyst (c) comprises an organotin catalyst or a bismuth catalyst.

In a fifth aspect, the present invention is a method of preparing macromer.
(1) This is a reaction process.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) The polyether dithiocarbonate polyol containing a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, an ethylenically unsaturated compound having a hydroxyl-reactive group and
(C) The method comprising the reaction step, optionally reacting in the presence of a catalyst, is of interest.

In a sixth aspect, the present invention comprises the polyether dithiocarbonate polyol (a) having an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, and a dithiocarbonate content of 0.10 to 15% by weight. In addition, in the reaction product contained in the polyether dithiocarbonate polyol (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and 2 to 7. Prepare a macromer of a fifth embodiment having a functional value, wherein the alkylene oxide (ii) comprises ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) comprises a composite metal cyanide complex catalyst. Target the method.

In a seventh aspect, in the present invention, the ethylenically unsaturated compound (b) having a hydroxyl-reactive group is methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. The macromer of the fifth or sixth aspect is prepared, which comprises an adduct of 2-isocyanatoethyl methacrylate, an isophorone diisocyanate and 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. Target the method.

In an eighth aspect, the present invention is directed to a method of preparing a macromer according to any of the fifth to seventh aspects, wherein the catalyst (c) comprises an organotin catalyst or a bismuth catalyst.

In a ninth aspect, the present invention is a preformed stabilizer.
(1) Of the macromer of any one of the first to fourth aspects,
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, the preformed stabilizer, which comprises a free radical polymerization product in the presence of a polymer control agent, is targeted.

In a tenth aspect, the present invention is directed to the preformed stabilizer of the ninth aspect, wherein the ethylenically unsaturated monomer (2) comprises styrene, acrylonitrile, or a mixture thereof.

In an eleventh aspect, the present invention comprises the free radical polymerization initiator (3) comprising a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. The preformed stabilizer of any of the ninth or tenth aspects is targeted.

In a twelfth aspect, the present invention comprises a ninth to ninth aspects in which the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. The preformed stabilizer of any of the eleven aspects is targeted.

In a thirteenth aspect, the present invention comprises the polymer control agent (5) comprising isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, or a mixture thereof. The preformed stabilizer of any of the ninth to twelfth aspects is targeted.

In a fourteenth aspect, the present invention is a method of preparing a preformed stabilizer.
(A) Free radical polymerization step
(1) The macromer obtained by any of the methods of the fifth to eighth aspects,
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, the method including the free radical polymerization step of performing free radical polymerization in the presence of a polymer control agent is targeted.

In a fifteenth aspect, the present invention is directed to a method of preparing a preformation stabilizer of the fourteenth aspect, wherein the ethylenically unsaturated monomer (2) comprises styrene, acrylonitrile, or a mixture thereof.

In a sixteenth aspect, the present invention comprises the free radical polymerization initiator (3) comprising a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. The subject is a method of preparing a preformed stabilizer of any of the 14th or 15th aspects.

In a seventeenth aspect, the present invention comprises the fourteenth to fourth aspects, wherein the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. The subject is a method of preparing a preformed stabilizer of any of the sixteen aspects.

In an eighteenth aspect, the present invention comprises the polymer control agent (5) comprising isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, or a mixture thereof. The method of preparing a preformed stabilizer according to any one of the 14th to 17th aspects is targeted.

In a nineteenth aspect, the present invention is a polymeric polyol
(A) Base polyol and
(B) Below:
(1) The macromer according to any one of the first to fourth aspects, and
(2) A component containing at least one of the preformed stabilizers according to any of the ninth to thirteenth aspects, and
(C) With at least one ethylenically unsaturated monomer,
(D) Free radical polymerization initiator and
(E) In some cases, the polymer polyol containing an in-situ free radical polymerization product in the presence of a polymer control agent is targeted.

In a twentieth aspect, the present invention is directed to the polymer polyol of the nineteenth aspect, wherein the polymer polyol has a solid content of 20-70% by weight.

In a twenty-first aspect, the present invention is in any of the nineteenth or twenty aspects, wherein the base polyol (A) has a functional value of 2-8 and an OH value of 10 mgKOH / g polyol to 180 mgKOH / g polyol. Polymer polyols of.

In a 22nd aspect, the present invention is directed to a polymeric polyol according to any of the 19th to 21st aspects, wherein the ethylenically unsaturated monomer (C) comprises styrene, acrylonitrile, or a mixture thereof.

In a twenty-third aspect, the present invention is directed to the polymeric polyol of the 22nd aspect, in which a mixture of styrene and acrylonitrile is present in a weight ratio of 80:20 to 20:80.

In a twenty-fourth aspect, the present invention comprises a polymer polyol according to any of the nineteenth to twenty-third aspects, wherein the free radical polymerization initiator (D) comprises a peroxide compound, an azo compound, or a mixture thereof. set to target.

In a twenty-fifth aspect, the present invention is a method of preparing a polymer polyol.
(I) Free radical polymerization step
(A) Base polyol and
(B) Below:
At least one of (1) macromer obtained by any of the fifth to eighth aspects and (2) preformed stabilizers obtained by any of the fourteenth to eighteenth aspects. Ingredients containing seeds and
(C) With at least one ethylenically unsaturated monomer,
(D) Free radical polymerization initiator and
(E) In some cases, the method including the free radical polymerization step of performing free radical polymerization in the presence of a polymer control agent is targeted.

In the 26th aspect, the present invention is directed to the method of preparing the polymer polyol of the 25th aspect, wherein the polymer polyol has a solid content of 20 to 70% by weight.

In a 27th aspect, the present invention is in any of the 25th or 26th aspects, wherein the base polyol (A) has a functional value of 2-8 and an OH value of 10 mgKOH / g polyol to 180 mgKOH / g polyol. The method for preparing a polymer polyol of the above is targeted.

In a 28th aspect, the present invention comprises a method of preparing a polymeric polyol according to any of the 25th to 27th aspects, wherein the ethylenically unsaturated monomer (C) comprises styrene, acrylonitrile, or a mixture thereof. set to target.

In a 29th aspect, the present invention relates to a method of preparing a polymeric polyol of the 28th aspect, in which a mixture of styrene and acrylonitrile is present in a weight ratio of 80:20 to 20:80.

In a thirtieth aspect, the present invention comprises a polymer polyol according to any of the 25th to 29th aspects, wherein the free radical polymerization initiator (D) comprises a peroxide compound, an azo compound, or a mixture thereof. The method of preparation is targeted.

In the 31st aspect, the present invention is a polyurethane foam.
(I) With diisocyanate and / or polyisocyanate components,
(II) With an isocyanate-reactive component containing the novel polymer polyol according to any of the 19th to 24th aspects.
(III) Catalyst,
(IV) Foaming agent and
(V) The polyurethane foam containing the reaction product in the presence of a surfactant is targeted.

In the 32nd aspect, the present invention is a method for preparing a polyurethane foam.
(I) Diisocyanate and / or polyisocyanate component
(II) An isocyanate-reactive component containing a novel polymer polyol obtained by any of the 25th to 30th aspects, and
(III) Catalyst,
(IV) Foaming agent and
(V) The above method includes the step of reacting in the presence of a surfactant.

The following examples further describe the details of the preparation and use of the compositions of the present invention. The present invention described in the above disclosure is not limited to any of the purposes or scope by these examples. Those skilled in the art will readily appreciate that these compositions can be prepared using the conditions of the following preparation procedures and known variations of the process. Unless otherwise stated, all temperatures are in degrees Celsius and all parts and percent are parts by weight and percent by weight, respectively.

In the examples, the following components were used.
Polypropylene oxide adduct of sorbitol containing 1:12% ethylene oxide and having a hydroxyl value of 33 mgKOH / g polyol. Polycarbonate 2: 20% ethylene oxide cap containing a hydroxyl value of 36 mgKOH / g polyol and having a viscosity. Is 820 mPa. Propylene oxide adduct of glycerin, s. polyol 3: a hydroxyl value of 57 mgKOH / g polyol and a viscosity of 465 mPa. S, propylene oxide adduct of glycerin polyol 4: glycerin / sorbitol started, containing about 81-82% propylene oxide and about 17-18% ethylene oxide and having an OH value of about 31.5 mgKOH / g polyol. Polyether polyol (glycerin / sorbitol started isocyanate polyol) Starter polyol 1: 143 mg KOH / g polyol, propylene oxide adduct of sorbitol Starter polyol 2: 198 mg KOH / g polyol, propylene oxide addition of sorbitol CS ₂ : Carbon disulfide, commercially available from Sigma Aldrich PCA: Isopropanol, polymer control agent TMI: Isopropenyldimethylbenzyl isocyanate (unsaturated aliphatic isocyanate) commercially available from Allnex as TMI (registered trademark) Isocyanate A: Approximately 42 weight Monomer MDI isocyanate B: 80% by weight is 2 of 4,4'-isomer of MDI, about 57% by weight of 2,4'-isomer of MDI and the balance is 2,2'-isomer of MDI. , 4-Isocyanate, 20% by weight 2,6-isomer and 48.3% NCO group content toluenediisocyanate TBPEH: Tertiary butylperoxy-2-ethylhexanoate initiator A: 2,2'-azobisisobutyronitrile, E.I. I. DuPont de Nemours and Co. Free radical polymerization initiator commercially available from VAZO 64 Initiator B: Tertiary amylperoxypivalate, Free radical polymerization initiator commercially available from AkzoNobel under the name Trigonox 125-C75 Catalyst A: Commercially available from Covetro LLC Composite metal cyanide catalyst catalyst B: bismas neodecanoate, commercially available from Vertellus under the name CosCat 83 Catalyst C: 70% by weight bis [2-dimethylaminoethyl] ether in 30% by weight dipropylene glycol , Amine catalyst, commercially available from Momentive Performance Materials as NIAX A-1 Catalyst D: 33% by weight diazabicyclooctane in 67% by weight dipropylene glycol, amine catalyst, commercially available from Momentive Performance Materials as NIAX A-33. Agent A: Silicone catalyst commercially available from Air Products as DC5043 DEOA-LF: Diethanolamine, commercially available foam crosslinker / foam modifier commercially available from Air Products Viscosity: mPa. At 25 ° C. Dynamic Viscosity Filtration Reported in s: Diluting 1 part by weight (eg, 200 grams) of a sample of polymer polyol with 2 parts by weight (eg, 400 grams) of anhydrous isopropanol removes any restrictions imposed by viscosity. By, and using a fixed amount of material for a fixed cross-sectional area of the screen (eg, 1/8 inch or 2.875 cm in diameter), 700 mesh of all solutions of polymer polyol and isopropanol by gravity. The filterability was determined by passing through the screen of. The 700 mesh screen was made of twill weave. The screen actually used had a nominal opening of 30 microns. The amount of sample that passes through the screen within 600 seconds is reported as a percentage, and a value of 100% indicates that more than 99 weight percent pass through the screen.
Method: OH value (hydroxyl value): The OH value is determined according to ASTM D4274-11, and is reported in mg [KOH] / g [polypoly].
Viscosity: Viscosity was measured at 25 ° C. with an Antonio-Paar SVM3000 viscometer. This has been demonstrated to provide results comparable to those produced by ASTM-D4878-15. The instrument was calibrated using a mineral oil reference standard of known viscosity.
Gel permeation chromatography:
The number average molecular weight and weight average molecular weight, Mn and Mw, respectively, were determined by gel permeation chromatography (GPC) using a method based on DIN 55672-1. The gel permeation chromatography uses a mixed bed column (Agilent PL gel; SDVB; 3 micron pore size: 1 × Mixed-E + 5 micron pore size: 2 × Mixed-D), differential refractometer (RI) detector. Chloroform was used as the eluent and calibrated with polyethylene glycol as the standard sample.
¹ H-NMR: The dithiocarbonate content is performed on a 400 MHz nuclear magnetic resonance (NMR) (Varian MR400) spectrometer in which ^{the sample is dissolved in deuterated chloroform and high resolution 1 H-NMR is used for characterization.} Was determined by.

The force-to-crush (FTC) is 12 inches x 12 inches x 4 using a standard IFD test and a 50 square inch (322.6 square cm) indentor foot. Measured against uncompressed foam sample in inches (30.5 cm x 30.5 cm x 10.2 cm). Foam height was measured by slowly lowering the indenter's paw until a resistance of 0.5 lbs (226.8 g) was detected. The indenter's foot was then pushed into the foam at 20 inches / min (50.8 cm / min) to 25% (75% compression) of its measured height and the force was immediately recorded. The indenter's foot was immediately returned to the height of the first foam and a second compression cycle and force measurements were started. This process was repeated 3 times to complete the measurement. Therefore, as a result of measuring the force three times, a first cycle (FTC1), a second cycle (FTC2), and a third cycle (FTC3) were obtained for each foam sample. The first measurement results provide an indicator of the force required to compress the foam first, but the difference between the second (FTC2) and third (FTC3) values is in opening the foam. the foam) Shows the degree of effect of the first compression cycle.

Modulation of polyol: Preparation of polyol 5:
A polyether polyol composition was prepared using the components and amounts shown in Table 1. In order to prepare the polyether polyol composition, the 1-L reactor was charged with the starter polyether polyol and the catalyst A at ambient temperature. The temperature of the reactor was raised to 130 ° C. and the starter mixture was dehydrated using vacuum distillation while sprinkling a small amount of nitrogen on the starter mixture. The reactor was then sealed under vacuum at 130 ° C. and an initial amount of PO equal to 10% by weight of the starter polyether polyol was charged into the reactor. The pressure in the reactor was monitored until the pressure dropped by 50% to show that the catalyst was active. When the catalyst was determined to be active, the temperature of the reactor was lowered to 100 ° C. PO supply was resumed at a rate sufficient to maintain the reaction pressure below 35 psig. When about 71% of the total weight of PO was supplied, the supply of CS ₂ was started at a speed of about 60% of the PO speed. When the desired amount of CS ₂ was supplied, the supply of PO was continued until the total amount of PO was supplied. After the addition of PO is complete, the reaction mixture is vacuum stripped at 130 ° C. to a OH value of 33.7 and a viscosity of 8091 mPa. A polyol 5 in which s and CS ₂ were 1.3% by weight (measured by NMR) was obtained.

Preparation of polyol 6:
Polyether polyol compositions were prepared using the ingredients and amounts listed in Table 2. To prepare a polyether polyol composition, a 20 kg reactor was charged with the starter polyether polyol and catalyst A at ambient temperature. The temperature of the reactor was raised to 130 ° C. and the starter mixture was dehydrated using vacuum distillation while sprinkling a small amount of nitrogen on the starter mixture. The temperature of the reactor was lowered to 100 ° C. and the reactor was sealed under vacuum. An initial amount of PO equal to 10% by weight of the starter polyether polyol was charged into the reactor. The pressure in the reactor was monitored until the pressure dropped by 50% to show that the catalyst was active. The supply of PO and EO was started at a rate sufficient to maintain the reaction pressure below 10 psig. When about 71% of the total weight of PO was supplied, the supply of EO was stopped and _{the supply of CS 2} was started at a speed of about 55% of the PO speed. When the desired amount of CS ₂ was supplied, the supply of PO was continued until the total amount of PO was supplied. After completing the addition of PO, the reaction mixture was vacuum stripped at 130 ° C. The reactor was cooled to 90 ° C., 7.2 g of Irganox 1076 was added to the reactor, and the mixture was stirred for 30 minutes to have an OH value of 32.6 and a viscosity of 4413 mPa. Obtained a polyol 6 in which s and CS ₂ were 2.5% by weight (measured by NMR).

Macromer preparation: Macromer A: A blend containing 61% by weight polyol 1 and 39% by weight polyol 5, isocyanate A (0.2% by weight) and catalyst B (100 ppm) by heating at 75 ° C. for 2 hours. It was adjusted.
Calculated carbon disulfide content = 0.6% by weight.
Macromer B: Polyol 6 Macromer C: A blend containing 65% by weight polyol 1 and 35% by weight polyol 6, isocyanate A (0.2% by weight), and catalyst B (100 ppm) is heated at 75 ° C. for 2 hours. Adjusted by
Carbon disulfide content = 0.9% by weight.
Macromer D: A blend of 65% polyol 1 and 35% by weight polyol 6.
Calculated carbon disulfide content = 0.9% by weight.
Macromer E: Prepared by heating polyol 1 containing TMI (0.6% by weight), isocyanate A (0.2% by weight) and catalyst B (100 ppm) at 75 ° C. for 4 hours.
Macromer F: A blend of 90% by weight Macromer C and 10% by weight Macromer E. Calculated carbon disulfide content = 0.8% by weight.

Preparation of preformed stabilizer (PFS):
Preformed stabilizers were prepared in a two-step reaction system. The two-stage reaction system includes a continuous stirring tank reactor (CSTR) (first stage) equipped with an impeller and four baffles, and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. The reactants were continuously pumped from the feed tank through the in-line static mixer to the reactor and then through the feed tube to the reactor and mixed well. The temperature of the reaction mixture was controlled to 120 ± 5 ° C. The product from the second stage reactor was continuously overflowed through a pressure regulator designed to control the pressure at each stage to 65 psig. The product, the preformed stabilizer, was then sent through the condenser to the recovery vessel. The formulations of the preformed stabilizers are disclosed in Table 3.

Preformed stabilizers AF were prepared from Macromer AF using the following formulations, respectively.

Preparation of polymer polyols:
This series of examples (Table 4) relates to the preparation of polymeric polyols. Polymer polyols were prepared in a two-step reaction system. The two-stage reaction system includes a continuous stirring tank reactor (CSTR) (first stage) equipped with an impeller and four baffles, and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. The reactants were continuously pumped from the feed tank through the in-line static mixer to the reactor and then through the feed tube to the reactor and mixed well. The temperature of the reaction mixture was controlled to 115 ± 5 ° C. The product from the second stage reactor was continuously overflowed through a pressure regulator designed to control the pressure at each stage to 45 psig. The product, the polymer polyol, was then sent through the condenser to the recovery vessel. The crude product was vacuum stripped to remove volatiles. The total solid content weight% in the product was calculated from the concentration of residual monomers measured on the crude polymer polyol before stripping.

General procedure for making foam:
The foams in Table 5 were prepared by mixing polyols, surfactants, water, catalysts and diethanolamine in flasks to create master blends. The desired amount of polymer polyol was then added to the cup containing the desired amount of master blend. The contents of the cup were mixed for 55 seconds. To the cup containing the mixture of master blend and polymer polyol, the desired amount of isocyanate component required to impart an isocyanate index of 100 was added. The contents of the cup were mixed for 5 seconds and the reaction mixture was quickly poured into a 150 ° F (65.5 ° C) water jacket mold. After 4.5 minutes, the foam is removed from the mold, passed through a cell-opening crushing device, and then placed in an oven at 250 ° F (121.1 ° C) for 30 minutes. It was post-cured. After aging for 24 hours in a controlled temperature and humidity laboratory, the foam was subjected to a physical property test. As can be seen from Table 5, the foams prepared from the PMPO (form 2) of the present invention had improved% settle (% settle) and compression force values.

The present invention has been described in detail above for purposes of illustration, but such details are solely for that purpose and are of the present invention unless they may be limited by the claims. It needs to be understood that variants can be made there by one of ordinary skill in the art without departing from the spirit and scope.

Claims (52)

Macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) With an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, optionally comprising a reaction product in the presence of at least one catalyst. The polyether dithiocarbonate polyol (a) has an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate polyol (a). ), The one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7, and the alkylene oxide ( The macromer according to claim 1, wherein ii) comprises ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) comprises a composite metal cyanide complex catalyst. The ethylenically unsaturated compound (b) having a hydroxyl-reactive group includes methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, isophorone diisocyanate and The macromer according to claim 1, which comprises an adduct of 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. The macromer according to claim 1, wherein the catalyst (c) contains an organotin catalyst or a bismuth catalyst. A method of preparing macromers
(1) This is a reaction process.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) The polyether dithiocarbonate polyol containing a copolymerization product in the presence of an alkoxylation catalyst.
(B) An ethylenically unsaturated compound having a hydroxyl-reactive group and
(C) The method comprising the reaction step, optionally reacting in the presence of at least one catalyst. The polyether dithiocarbonate polyol (a) has an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate polyol (a). ), The one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7, and the alkylene oxide ( The method of claim 5, wherein ii) comprises ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) comprises a composite metal cyanide complex catalyst. The ethylenically unsaturated compound (b) having a hydroxyl-reactive group includes methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, isophorone diisocyanate and The method of claim 5, comprising an adduct of 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. The method of claim 5, wherein the catalyst (c) comprises an organotin catalyst or a bismuth catalyst. A preformed stabilizer
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, optionally comprising a reaction product in the presence of a catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) The preformed stabilizer, optionally comprising a free radical polymerization product in the presence of a polymer regulator. The polyether dithiocarbonate polyols (1) and (a) have an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate. In the reaction products contained in the polyols (1) and (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7. The preformed stabilizer according to claim 9, wherein the alkylene oxide (ii) contains ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) contains a composite metal cyanide complex catalyst. The ethylenically unsaturated compounds (1) and (b) having a hydroxyl-reactive group are methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, The preformed stabilizer according to claim 9, comprising an adduct of isophorone diisocyanate and 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. The preformed stabilizer according to claim 9, wherein the catalyst (c) contains an organotin catalyst or a bismuth catalyst. The preformed stabilizer according to claim 9, wherein the ethylenically unsaturated monomer (2) contains styrene, acrylonitrile, or a mixture thereof. The preformation of claim 9, wherein the free radical polymerization initiator (3) comprises a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. Stabilizer. The preformed stabilizer according to claim 9, wherein the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. The preformed stable according to claim 9, wherein the polymer control agent (5) comprises isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, or a mixture thereof. Agent. A method of preparing a preformed stabilizer,
(A) Free radical polymerization step
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05 to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, optionally containing a reaction product in the presence of a catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) The method comprising the free radical polymerization step, which optionally performs free radical polymerization in the presence of a polymer control agent. The polyether dithiocarbonate polyols (1) and (a) have an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate. In the reaction products contained in the polyols (1) and (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7. 17. The method of claim 17, wherein the alkylene oxide (ii) comprises ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) comprises a composite metal cyanide complex catalyst. The ethylenically unsaturated compounds (1) and (b) having a hydroxyl-reactive group are methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, 17. The method of claim 17, comprising an adduct of isophorone diisocyanate and 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. 17. The method of claim 17, wherein the catalyst (c) comprises an organotin catalyst or a bismuth catalyst. 17. The method of claim 17, wherein the ethylenically unsaturated monomer (2) comprises styrene, acrylonitrile, or a mixture thereof. The method of claim 17, wherein the free radical polymerization initiator (3) comprises a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. 17. The method of claim 17, wherein the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. 17. The method of claim 17, wherein the polymer control agent (5) comprises isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, or a mixture thereof. It is a polymer polyol
(A) Base polyol and
(B) Below:
(1) A macromer containing a dithiocarbonate functional group.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, which optionally comprises a reaction product in the presence of a catalyst, and
(2) Preformed stabilizer
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, optionally comprising a reaction product in the presence of a catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
A component comprising at least one of the preformed stabilizers, including (4) optionally a liquid diluent, and (5) optionally a free radical polymerization product in the presence of a polymer control agent.
(C) With at least one ethylenically unsaturated monomer,
(D) Free radical polymerization initiator and
(E) The polymer polyol, optionally comprising an in-situ free radical polymerization product in the presence of a polymer control agent. The polyether dithiocarbonate polyols (1) and (a) have an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate. In the reaction products contained in the polyols (1) and (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7. The polymer polyol according to claim 25, wherein the alkylene oxide (ii) contains ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) contains a composite metal cyanide complex catalyst. The ethylenically unsaturated compounds (1) and (b) having a hydroxyl-reactive group are methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, 25. The polymer polyol according to claim 25, which comprises an adduct of isophorone diisocyanate and 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. The polymer polyol according to claim 25, wherein the catalyst (c) contains an organotin catalyst or a bismuth catalyst. The polymer polyol according to claim 25, wherein the ethylenically unsaturated monomer (2) contains styrene, acrylonitrile, or a mixture thereof. The polymer polyol according to claim 25, wherein the free radical polymerization initiator (3) comprises a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. 25. The polymer polyol according to claim 25, wherein the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. The polymer polyol according to claim 25, wherein the polymer control agent (5) comprises isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride or a mixture thereof. The polymer polyol according to claim 25, which has a solid content of 20 to 70% by weight. The polymer polyol according to claim 25, wherein the base polyol (A) has a functional value of 2 to 8 and an OH value of 10 mgKOH / g polyol to 180 mgKOH / g polyol. The polymer polyol according to claim 25, wherein the ethylenically unsaturated monomer (C) contains styrene, acrylonitrile, or a mixture thereof. The polymer polyol according to claim 35, wherein a mixture of styrene and acrylonitrile is present in a weight ratio of 80:20 to 20:80. The polymer polyol according to claim 25, wherein the free radical polymerization initiator (D) contains a peroxide compound, an azo compound, or a mixture thereof. The method for preparing the polymer polyol according to claim 25.
(I) Free radical polymerization step
(A) Base polyol and
(B) Below:
(1) A macromer having a dithiocarbonate functional group.
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) The macromer, which optionally comprises a reaction product in the presence of a catalyst, and
(2) Preformed stabilizer
(1) Being a macromer
(A) A polyether dithiocarbonate polyol having an equivalent of 230 Da to 5600 Da and a functional value of 1 to 8 and a dithiocarbonate content of 0.05% by weight to 20% by weight.
(I) One or more starter-polyether polyols having an equivalent of less than 1000 Da, an OH value greater than 56 mgKOH / g polyol and a functional value of 1-8.
(Ii) With alkylene oxide
(Iii) Carbon disulfide and
Of the reaction mixture containing
(Iv) Of the polyether dithiocarbonate polyol, which comprises a copolymerization product in the presence of an alkoxylation catalyst.
(B) In some cases, with an ethylenically unsaturated compound having a hydroxyl-reactive group,
(C) Of the macromer, optionally comprising a reaction product in the presence of a catalyst.
(2) With at least one ethylenically unsaturated monomer,
(3) Free radical polymerization initiator and
(4) In some cases, a liquid diluent and
(5) In some cases, a component containing at least one of the preformed stabilizers, including a free radical polymerization product in the presence of a polymer control agent.
(C) With at least one ethylenically unsaturated monomer,
(D) Free radical polymerization initiator and
(E) The method, which comprises the free radical polymerization step, optionally subject to free radical polymerization in the presence of a polymer control agent. The polyether dithiocarbonate polyols (1) and (a) have an equivalent of 280 Da to 5400 Da, a functional value of 2 to 7, a dithiocarbonate content of 0.10 to 15% by weight, and the polyether dithiocarbonate. In the reaction products contained in the polyols (1) and (a), one or more starter polyether polyols (i) have an OH value of at least 112 mgKOH / g polyol to 1850 mgKOH / g polyol and a functional value of 2 to 7. 38. The method of claim 38, wherein the alkylene oxide (ii) comprises ethylene oxide and / or propylene oxide, and the alkoxylation catalyst (iv) comprises a composite metal cyanide complex catalyst. The ethylenically unsaturated compounds (1) and (b) having a hydroxyl-reactive group are methyl methacrylate, ethyl methacrylate, maleic anhydride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, 38. The method of claim 38, comprising an adduct of isophorone diisocyanate and 2-hydroxyethyl methacrylate, an adduct of toluene diisocyanate and 2-hydroxypropyl acrylate, or a mixture thereof. 38. The method of claim 38, wherein the catalyst (c) comprises an organotin catalyst or a bismuth catalyst. 38. The method of claim 38, wherein the ethylenically unsaturated monomer (2) comprises styrene, acrylonitrile, or a mixture thereof. 38. The method of claim 38, wherein the free radical polymerization initiator (3) comprises a peroxide-based initiator, an azo-based initiator, or a mixture of a peroxide-based initiator and an azo-based initiator. 38. The method of claim 38, wherein the diluent (4) comprises isopropanol, a polyol having an OH value of 20 mgKOH / g polyol to 280 mgKOH / g polyol, or a mixture of monool and polyol. 38. The method of claim 38, wherein the polymer control agent (5) comprises isopropanol, toluene, ethylbenzene, dodecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride, or a mixture thereof. 38. The method of claim 38, wherein the polymer polyol has a solid content of 20-70% by weight. 38. The method of claim 38, wherein the base polyol (A) has a functional value of 2-8 and an OH value of 10 mgKOH / g polyol to 180 mgKOH / g polyol. 38. The method of claim 38, wherein the ethylenically unsaturated monomer (C) comprises styrene, acrylonitrile, or a mixture thereof. The method of claim 48, wherein the mixture of styrene and acrylonitrile is present in a weight ratio of 80:20 to 20:80. 38. The method of claim 38, wherein the free radical polymerization initiator (D) comprises a peroxide compound, an azo compound, or a mixture thereof. Polyurethane foam
(I) Of the diisocyanate or polyisocyanate component,
(II) With an isocyanate-reactive component containing the polymer polyol according to claim 25,
(III) Catalyst,
(IV) Foaming agent and
(V) The polyurethane foam comprising a reaction product in the presence of a surfactant. A method of preparing polyurethane foam,
(I) Diisocyanate or polyisocyanate component
(II) The isocyanate-reactive component containing the polymer polyol according to claim 25,
(III) Catalyst,
(IV) Foaming agent and
(V) The method comprising a step of reacting in the presence of a surfactant.